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21.
Wan S Wu F Rech JC Green ME Balachandran R Horne WS Day BW Floreancig PE 《Journal of the American Chemical Society》2011,133(41):16668-16679
The potent cytotoxins pederin and psymberin have been prepared through concise synthetic routes (10 and 14 steps in the longest linear sequences, respectively) that proceed via a late-stage multicomponent approach to construct the N-acyl aminal linkages. This route allowed for the facile preparation of a number of analogs that were designed to explore the importance of the alkoxy group in the N-acyl aminal and functional groups in the two major subunits on biological activity. These analogs, including a pederin/psymberin chimera, were analyzed for their growth inhibitory effects, revealing several new potent cytotoxins and leading to postulates regarding the molecular conformational and hydrogen bonding patterns that are required for biological activity. Second generation analogs have been prepared based on the results of the initial assays and a structure-based model for the binding of these compounds to the ribosome. The growth inhibitory properties of these compounds are reported. These studies show the profound role that organic chemistry in general and specifically late-stage multicomponent reactions can play in the development of unique and potent effectors for biological responses. 相似文献
22.
Dhas DA Joe IH Roy SD Balachandran S 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2011,79(5):993-1003
Vibrational analysis of the thionocarbamate fungicide tolnaftate which is antidermatophytic, antitrichophytic and antimycotic agent, primarily inhibits the ergosterol biosynthesis in the fungus, was carried out using NIR FT-Raman and FTIR spectroscopic techniques. The equilibrium geometry, various bonding features, harmonic vibrational wavenumbers and torsional potential energy surface (PES) scan studies have been computed using density functional theory method. The detailed interpretation of the vibrational spectra has been carried out with the aid of VEDA.4 program. Vibrational spectra, natural bonding orbital (NBO) analysis and optimized molecular structure show the clear evidence for electronic interaction of thionocarbamate group with aromatic ring. Predicted electronic absorption spectrum from TD-DFT calculation has been compared with the UV-vis spectrum. The Mulliken population analysis on atomic charges and the HOMO-LUMO energy were also calculated. Vibrational analysis reveals that the simultaneous IR and Raman activation of the C-C stretching mode in the phenyl and naphthalene ring provide evidence for the charge transfer interaction between the donor and acceptor groups and is responsible for its bioactivity as a fungicide. 相似文献
23.
We derive a set of sufficient conditions for the existence of solutions of a Hammerstein integral equation. 相似文献
24.
Shin Y Fournier JH Brückner A Madiraju C Balachandran R Raccor BS Edler MC Hamel E Sikorski RP Vogt A Day BW Curran DP 《Tetrahedron》2007,63(35):8537-8562
Total syntheses of (−)-dictyostatin, 6,16-bis-epi-dictyostatin, 6,14,19-tris-epi-dictyostatin, and a number of other isomers and analogs are reported. Three main fragments—top, middle, and bottom—were first assembled and then joined by olefination or anionic addition reactions. After appending the two dienes at either end of the molecule, macrolactonization and deprotection completed the syntheses. The work proves both the relative and absolute configurations of (−)-dictyostatin. The compounds were evaluated by cell-based measurements of increased microtubule mass and antiproliferative activity, and in vitro tubulin polymerization assays as well as competitive assays with paclitaxel for its binding site on microtubules. These assays showed dictyostatin to be the most potent of the agents and further showed that the structural alterations caused from 20- to >1000-fold decreases in activity. 相似文献
25.
Legislation in several countries restricting noise emitted by individual road vehicles recommends the use of international standard ISO R362, or something very similar, as a standard. This is a pass-by test with strict conditions laid down regarding the test site, weather conditions, and so on. As such it is not well suited for simple routine and quick roadside enforcement of vehicle noise. This paper describes some initial work aimed at clarifying and resolving a number of the difficulties commonly encountered with stationary tests and describes a procedure which gives good correlation with the ISO pass-by test and may lead to a test which could be used for routine service check and roadside enforcement. 相似文献
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28.
The Raman spectrum of polycrystalline calcium titanate prepared by a liquid mix technique and heated to 800°C has been recorded at room temperature using an argon-ion laser as exciter. The observed spectrum was interpreted on the basis of factor-group C2V. Not all of the Raman active modes predicted by factor group analysis were observed and this could be due to: over-lapping of bands, or very low polarizabilities of some of the modes or masking of the weak bands by intense bands. The band at 639 cm?1 is tentatively assigned to the TiO symmetric stretching vibration (γ1) and the bands at 495 and 471 cm?1 to torsional modes. The bands in the region 180–340 cm?1 are assigned to the OTiO bending modes and the 155 cm?1 band to the Ca(TiO3) lattice mode. The observed Raman bands are compared with the available infrared absorption data and, as expected, some coincidences in frequencies are seen for this compound with a noncentrosymmetric structure. 相似文献
29.
Non-perovskite SrFeCo0.5O
x
(SFC2) was found to have high electronic and ionic conductivities as well as structural stability. At 800°C in air, total
and ionic conductivities of 17 and 7 S·cm−1 were measured, respectively; the ionic transference number was calculated to be ≈0.4. This material is unique because of
its high electronic conductivity and comparable electronic and ionic transference numbers. X-ray diffraction analysis showed
that air-sintered SFC2 consists of three phase components, ≈75 wt% , ≈20 wt% perovskite , and ≈5 wt% rock salt CoO. Argon-annealed SFC2 contains brownmillerite Sr2(Fe1−x
Co
x
)2O5 and rock salt CoO. Dense SFC2 membranes were able to withstand large pO2 gradients and retain mechanical strength. A 2.9-mm-thick disk membrane was tested in a gas-tight electrochemical cell at
900°C; an oxygen permeation flux rate ≈2.5 cm3(STP)·cm−2·min−1 was measured. A dense thin-wall tubular membrane of 0.75-mm thickness was tested in a methane conversion reactor for over
1,000 h. At 950°C, the oxygen permeation flux rate was ≈10 cm3(STP)·cm−2·min−1 when the SFC2 thin-wall membrane was exposed with one side to air and the other side to 80% methane balanced with inert gas.
Results from these two independent experiments agreed well. The SFC2 material is a good candidate as dense ceramic membranes
for oxygen separation from air or for use in methane conversion reactors. 相似文献
30.
Sambath Muniyagounder Balachandran Krishnan 《Journal of Applied Analysis & Computation》2013,3(1):71-80
In this paper, we investigate the spatiotemporal dynamics of a ratio-dependent predator-prey model with cross diffusion incorporating proportion of prey refuge. First we get the critical lines of Hopf and Turing bifurcations in a spatial domain by using mathematical theory. More specifically, the exact Turing region is given in a two parameter space. Also we perform a series of numerical simulations. The obtained results reveal that this system has rich dynamics, such as spotted, stripe and labyrinth patterns which show that it is useful to use the predator-prey model to reveal the spatial dynamics in the real world. 相似文献